Material having a conductive pattern; and a material and method for making a conductive pattern

ABSTRACT

A material having a conductive pattern, the material comprising a support and a conductive element, the conductive element being 500 nm thick or less and containing a polyanion and an intrinsically conductive polymer, characterized in that one surface of the conductive element is an outermost surface of the material and the other surface of the conductive element is contiguous with a patterned surface, the patterned surface consisting of at least two types of surface element, and those parts of the conductive element contiguous with a type A surface element exhibiting a surface resistance at least a factor of ten greater than those parts of the conductive element contiguous with a type B surface element.

This applications is a divisional application Ser. No. 10/175,989, filedJun. 20, 2002, now U.S. Pat. No. 6,746,751, which claims the benefit ofU.S. Provisional Application No. 60/350,731 filed Jan. 22, 2002, whichis herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a material and a method for making aconductive pattern.

BACKGROUND OF THE INVENTION

Transparent ITO (indium-tin oxide) electrodes are used for thefabrication of flexible LC displays, electroluminescent devices andphotovoltaic cells. These electrodes are made by vacuum sputtering ITOonto a substrate. This method involves high temperatures, up to 250° C.,and therefore glass substrates are generally used. The range ofpotential applications is limited, because of the high fabricationcosts, the low flexibility (pliability) and stretchability, due to thebrittleness of the ITO layer and the glass substrate. Therefore interestis growing in all-organic devices, comprising plastic resins as asubstrate and organic intrinsically conductive polymer layers aselectrodes. Such plastic electronics allow the realization of low costdevices with new properties (Physics World, March 1999, p.25-39).Flexible plastic substrates can be provided with an intrinsicallyconductive polymer layer by continuous roller coating methods (comparedto batch process such as sputtering) and the resulting organicelectrodes enable the fabrication of electronic devices with higherflexibility and a lower weight.

The production and use of intrinsically conductive polymers such aspolypyrrole, polyaniline, polyacetylene, polyparaphenylene,polythiophene, polyphenylenevinylene, polythienylenevinylene andpolyphenylenesulphide are known in the art.

EP-A 440 957 discloses dispersions of polythiophenes, constructed fromstructural units of formula (I):

in which R¹ and R² independently of one another represent hydrogen or aC₁₋₄-alkyl group or together form an optionally substitutedC₁₋₄-alkylene residue, in the presence of polyanions. Furthermore,EP-A-686 662 discloses mixtures of A) neutral polythiophenes with therepeating structural unit of formula (I),

in which R¹ and R² independently of one another represent hydrogen or aC₁₋₄-alkyl group or together represent an optionally substitutedC₁₋₄-alkylene residue, preferably an optionally with alkyl groupsubstituted methylene, an optionally with C₁₋₁₂-alkyl or phenyl groupsubstituted 1,2-ethylene residue or a 1,2-cyclohexene residue, and B) adi- or polyhydroxy- and/or carboxy groups or amide or lactam groupcontaining organic compound; and conductive coatings therefrom which aretempered at elevated temperature, preferably between 100 and 250° C.,during preferably 1 to 90 seconds to increase their resistancepreferably to <300 ohm/square.

Coated layers of organic intrinsically conductive polymers can bestructured into patterns using known microlithographic techniques. InWO-A-97 18944 a process is described wherein a positive or negativephotoresist is applied on top of a coated layer of an organicintrinsically conductive polymer, and after the steps of selectivelyexposing the photoresist to UV light, developing the photoresist,etching the intrinsically conductive polymer layer and finally strippingthe non-developed photoresist with an organic solvent, a patterned layeris obtained. A similar technique has been described in 1988 in SyntheticMetals, volume 22, pages 265-271 for the design of an all-organicthin-film transistor. Such methods are cumbersome as they involve manysteps and require the use of hazardous chemicals.

WO 01/88958 published on Nov. 22, 2001 discloses a method of forming apattern of a functional material on a substrate comprising: applying afirst pattern of a first material to said substrate; and applying asecond functional material to said substrate and said first material,wherein said first material, said second functional material, and saidsubstrate interact to spontaneously form a second pattern of said secondfunctional material on said substrate, to thereby form a pattern of afunctional material a substrate.

ASPECTS OF THE INVENTION

It is an aspect of the present invention to provide a process for makinga conductive pattern, which does not require the use of hazardouschemicals.

It is a further aspect of the present invention to provide a materialhaving a conductive pattern without a development step.

It is a further aspect of the present invention to provide a materialhaving a conductive element that can be processed to a conductivepattern by a simple, convenient method which involves a low number ofsteps and which does not require the use of hazardous chemicals.

Further aspects and advantages of the invention will become apparentfrom the description hereinafter.

SUMMARY OF THE INVENTION

A conductive pattern can be realized with the materials of the presentinvention, which are optionally conductivity enhanced, withoutimage-wise heating or exposure and with optionally a single wetprocessing step, and optional conductivity enhancement. No etchingliquids or organic solvents are required. Furthermore, a conductivepattern is realized in layers ≦500 nm thick without processing.

Aspects of the present invention are realized by a material having aconductive pattern, the material comprising a support and a conductiveelement, the conductive element being 500 nm thick or less andcontaining a polyanion and an intrinsically conductive polymer,characterized in that one surface of the conductive element is anoutermost surface of the material and the other surface of theconductive element is contiguous with a patterned surface, the patternedsurface consisting of at least two types of surface element, and thoseparts of the conductive element contiguous with a type A surface elementexhibiting a surface resistance at least a factor of ten greater thanthose parts of the conductive element contiguous with a type B surfaceelement.

Aspects of the present invention are also realized by a material formaking a conductive pattern, the material comprising a support and aconductive element, the conductive element containing a polyanion and anintrinsically conductive polymer, characterized in that one surface ofthe conductive element is an outermost surface of the material, theother surface of the conductive element is contiguous with a patternedsurface, the patterned surface consisting of at least two types ofsurface element, and those parts of the conductive element contiguouswith one type of the surface elements are capable of being at leastpartially removed by a developer.

Aspects of the present invention are also realized by a method of makinga conductive pattern on a support comprising the steps of: providing amaterial for making a conductive pattern as disclosed above; processingthe material with a developer, thereby at least partially removing thoseparts of the conductive element contiguous with one type of the surfaceelements; and optionally treating the material to increase theelectroconductivity of the material.

Further advantages and embodiments of the present invention will becomeapparent from the following description.

DETAILED DESCRIPTION OF THE INVENTION Definitions

The term “support” means a “self-supporting material” so as todistinguish it from a “layer” which may be coated on a support, butwhich is itself not self-supporting. It also includes any treatmentnecessary for, or layer applied to aid, adhesion to the differentiableelement.

The term conductive means having a surface resistance or 10¹¹ Ω/squareor less and is a generic term including both the terms antistatic andelectroconductive.

The term electroconductive means having a surface resistance below 10⁶Ω/square. Antistatic materials have surface resistances in the rangefrom 10⁶ to 10¹¹ Ω/square and cannot be used as an electrode.

The term conductive pattern means a pattern with elements which havedifferent surface resistances.

The term intrinsically conductive polymer means organic polymers whichhave (poly)-conjugated π-electron systems (e.g. double bonds, aromaticor heteroaromatic rings or triple bonds) and whose conductive propertiesare not influenced by environmental factors such as relative humidity.

The term continuous layer refers to a layer in a single plane coveringthe whole area of the support and not necessarily in direct contact withthe support.

The term non-continuous layer refers to a layer in a single plane notcovering the whole area of the support and not necessarily in directcontact with the support.

Conductivity enhancement refers to a process in which the conductivityis enhanced e.g. by contact with high boiling point liquids such as di-or polyhydroxy- and/or carboxy groups or amide or lactam groupcontaining organic compound optionally followed by heating at elevatedtemperature, preferably between 100 and 250° C., during preferably 1 to90 seconds, results in conductivity increase. Alternatively in the caseof aprotic compounds with a dielectric constant ≧15, e.g.N-methyl-pyrrolidinone, temperatures below 100° C. can be used. Suchconductivity enhancement is observed with polythiophenes and can takeplace during the preparation of the outermost layer or subsequently.Particularly preferred liquids for such treatment areN-methyl-pyrrolidinone and diethylene glycol such as disclosed in EP-A686 662 and EP-A 1 003 179.

The term removability as used in the description and claims of thepresent invention means mechanically removable in the absence of aliquid or removable with the application of a liquid with or without thesimultaneous or subsequent use of rubbing or other mechanical removalmeans. The application of liquid can dissolve, swell or disperse theoutermost layer according to the present invention such that removal isrealized or enabled.

The term multidiazonium salt includes all compounds with at least twogroups with two nitrogen atoms bonded together with a double or triplebond, such groups including —N≡N⁺ and —N═N—R groups e.g. —N═N—SO₃Mgroups.

The term resin comprising a diazonium salt means a resin with groupswith two nitrogen atoms bonded together with a double or triple bond,such groups including —N≡N⁺ and —N═N—R groups e.g. —N═N—SO₃M groups.

The term proteinaceous means pertaining to any material having a proteinbase.

Material Having a Conductive Pattern

The material having a conductive pattern, according to the presentinvention, has a conductive element 500 nm or less thick contiguous witha patterned surface consisting of at least two types of surface element.Contact of these types of surface elements with the conductive elementresults in a lower surface resistance of those parts of the conductiveelement contiguous with one type of surface element than those parts ofthe conductive element contiguous with another type of surface element.Each type of surface element lies in the same plane, but all surfaceelements need not lie in the same plane.

The reason for this effect is unknown, but the effect is only observedfor conductive elements with a thickness of 500 nm or less. At suchthicknesses, the thinness of conductive element means that theinterfacial forces between the conductive element and the patternedsurface during coating and during and after drying will have aconsiderable effect on the properties of the electroconductive layer andhence possibly on the surface resistance thereof.

According to a first embodiment of a material having a conductivepattern, according to the present invention, the conductive pattern isan electroconductive pattern.

According to a second embodiment of a material having a conductivepattern, according to the present invention, the patterned surface isplanar or non-planar. A non-planar pattern can be produced usingconventional printing techniques, such as screen printing, offsetprinting, flexographic printing and ink jet printing, with conventionalresist technology, plasma etching techniques.

According to a third embodiment of a material having a conductivepattern, according to the present invention, the patterned surface isplanar and is the surface of the support or a patternwise treatedcontinuous layer. The patterning of the continuous layer or the supportcan, for example, be realized by patternwise treatment with an electronbeam, ion implantation, a corona discharge or a glow discharge.

According to a fourth embodiment of a material having a conductivepattern, according to the present invention, the patterned surface isplanar and is a continuous layer which is patternwise treated with acorona discharge or a glow discharge.

According to a fifth embodiment of a material having a conductivepattern, according to the present invention, the patterned surface isnon-planar and consists of a non-continuous layer provided on acontinuous layer or on the support. The non-continuous layer can beproduced using conventional printing techniques, such as screenprinting, offset printing, flexographic printing and ink jet printing,with conventional resist technology, plasma etching techniques.

According to a sixth embodiment of a material having a conductivepattern, according to the present invention, the conductive element hasa surface resistance lower than 10⁶ Ω/square.

According to a seventh embodiment of a material having a conductivepattern, according to the present invention, the conductive element hasa surface resistance lower than 10⁴ Ω/square.

According to an eighth embodiment of a material having a conductivepattern, according to the present invention, the conductive element hasa surface resistance capable of being lower than 10⁶ Ω/square aftertreatment in a so-called conductivity enhancement process.

According to a ninth embodiment of a material having a conductivepattern, according to the present invention, the conductive elementfurther contains a multidiazonium salt, a resin comprising a diazoniumsalt or both a multidiazonium salt and a resin comprising a diazoniumsalt, which reduces the removability of those parts of the conductiveelement contiguous with the patterned surface not removed during thedevelopment step. Combinations of resins comprising a diazonium salt canalso be used.

Material for Making a Conductive Pattern

Aspects of the present invention are realized by a material for making aconductive pattern, the material comprising a support and a conductiveelement, the conductive element containing a polyanion and anintrinsically conductive polymer, characterized in that one surface ofthe conductive element is an outermost surface of the material, theother surface of the conductive element is contiguous with a patternedsurface, the patterned surface consisting of at least two types ofsurface element, and those parts of the conductive element contiguouswith one type of surface element are capable of being at least partiallyremoved by a developer. The term patterned surface, according to thematerial for making a conductive pattern, according to the presentinvention, means a surface with at least two types of surface elementsexhibiting different abilities to adhere to the contiguous conductiveelement. This variation in the ability of elements of the surface toadhere to the contiguous conductive element over the patterned surfaceforms a pattern.

According to a first embodiment of a material for making a conductivepattern, according to the present invention, the conductive pattern isan electroconductive pattern.

According to a second embodiment of a material for making a conductivepattern, according to the present invention, the patterned surface isplanar or non-planar. A non-planar pattern can be produced usingconventional printing techniques, such as screen printing, offsetprinting, flexographic printing and ink jet printing, with conventionalresist technology, plasma etching techniques.

According to a third embodiment of a material for making a conductivepattern, according to the present invention, the patterned surface isplanar and is the surface of the support or a patternwise treatedcontinuous layer. The patterning of the continuous layer or the supportcan, for example, be realized by patternwise treatment with an electronbeam, ion implantation, a corona discharge or a glow discharge.

According to a fourth embodiment of a material for making a conductivepattern, according to the present invention, the patterned surface is acontinuous layer which is patternwise treated with a corona discharge ora glow discharge.

According to a fifth embodiment of a material for making a conductivepattern, according to the present invention, the patterned surface isnon-planar and consists of a non-continuous layer provided on acontinuous layer or on the support. The non-continuous layer can beproduced using conventional printing techniques, such as screenprinting, offset printing, flexographic printing and ink jet printing,with conventional resist technology, plasma etching techniques.

According to a sixth embodiment of a material for making a conductivepattern, according to the present invention, the conductive elementfurther contains an element which upon light exposure produces changesin the properties or composition of the exposed parts of the element.

Examples of such changes in the properties or composition of the exposedparts of the element are exposure-induced crosslinking; exposure-induceddecrease of solubility; and exposure-induced increase of adhesion to thepatterned surface of the non-removed parts of the conductive element.

According to a seventh embodiment of a material for making a conductivepattern, according to the present invention, the conductive element hasa surface resistance lower than 10⁶ Ω/square.

According to an eighth embodiment of a material for making a conductivepattern, according to the present invention, the conductive element hasa surface resistance lower than 10⁴ Ω/square.

A conductive pattern can be rendered electroconductive by apost-treatment process, such as a conductivity enhancement process.According to a ninth embodiment of a material for making a conductivepattern, according to the present invention, the conductive element hasa surface resistance capable of being lower than 10⁶ Ω/square aftertreatment in a so-called conductivity enhancement process.

Conductive

The term “conductive” is related to the electric resistance of thematerial. The electric resistance of a layer is generally expressed interms of surface resistance R_(s) (unit Ω; often specified as Ω/square).Alternatively, the conductivity may be expressed in terms of volumeresistivity R_(v)=R_(s)·d, wherein d is the thickness of the layer,volume conductivity k_(v)=1/R_(v) [unit: S(iemens)/cm] or surfaceconductance k_(s)=1/R_(s) [unit: S(iemens).square].

All values of electric resistance presented herein are measuredaccording to one of the following methods. In the first method thesupport coated with the electroconductive outermost layer is cut toobtain a strip having a length of 27.5 cm and a width of 35 mm and stripelectrodes are applied over its width at a distance of 10 cmperpendicular to the edge of the strip. The electrodes are made of anintrinsically conductive polymer, ECCOCOAT CC-2 available from Emerson &Cumming Speciality polymers. Over the electrode a constant potential isapplied and the current flowing through the circuit is measured on apico-amperometer KEITHLEY 485. From the potential and the current,taking into account the geometry of the area between the electrodes, thesurface resistance in Ω/square is calculated.

In the second method, the surface resistance was measured by contactingthe outermost layer with parallel copper electrodes each 35 mm long and35 mm apart capable of forming line contacts, the electrodes beingseparated by a teflon insulator. This enables a direct measurement ofthe surface resistance.

Support

Supports for use according to the present invention include polymericfilms, silicon, ceramics, oxides, glass, polymeric film reinforcedglass, glass/plastic laminates, metal/plastic laminates, paper andlaminated paper, optionally treated, provided with a subbing layer orother adhesion promoting means to aid adhesion to the light-exposuredifferentiable element. Suitable polymeric films are poly(ethyleneterephthalate), poly(ethylene naphthalate), polystyrene,polyethersulphone, polycarbonate, polyacrylate, polyamide, polyimides,cellulosetriacetate, polyolefins and polyvinylchloride, optionallytreated by corona discharge or glow discharge or provided with a subbinglayer.

Conductive Element

The conductive element used in the material of the present inventioncontains an intrinsically conductive polymer and can consist of one ormore continuous layers.

Intrinsically Conductive Polymer

The intrinsically conductive polymers used in the present invention canbe any intrinsically conductive polymer known in the art e.g.polyacetylene, polypyrrole, polyaniline, polythiophene, etc. Detailsabout suitable intrinsically conductive polymers can be found intextbooks, such as “Advances in Synthetic Metals”, ed. P. Bernier, S.Lefrant, and G. Bidan, Elsevier, 1999; “Intrinsically ConductingPolymers: An Emerging Technology”, Kluwer (1993); “Conducting PolymerFundamentals and Applications, A Practical Approach”, P. Chandrasekhar,Kluwer, 1999; and “Handbook of Organic Conducting Molecules andPolymers”, Ed. Walwa, Vol. 1-4, Marcel Dekker Inc. (1997).

According to a tenth embodiment of the material having a conductivepattern, according to the present invention, or a tenth embodiment orthe material for making a conductive pattern, according to the presentinvention, the intrinsically conductive polymer is a polyanion and apolymer or copolymer of a substituted or unsubstituted thiophene.

According to an eleventh embodiment of the material having a conductivepattern, according to the present invention, or an eleventh embodimentor the material for making a conductive pattern, according to thepresent invention, the intrinsically conductive polymer is a substitutedor unsubstituted thiophene represented by formula (I):

in which n is larger than 1 and each of R¹ and R² independentlyrepresents hydrogen or an optionally substituted C₁₋₄ alkyl group ortogether represent an optionally substituted C₁₋₄ alkylene group or anoptionally substituted cycloalkylene group, preferably an ethylenegroup, an optionally alkyl-substituted methylene group, an optionallyC₁₋₁₂ alkyl- or phenyl-substituted ethylene group, a 1,3-propylene groupor a 1,2-cyclohexylene group.

The preparation of such a polythiophene and of aqueous dispersionscontaining such a polythiophene and a polyanion is described in EP-A-440957 and corresponding U.S. Pat. No. 5,300,575. Basically the preparationof polythiophene proceeds in the presence of polymeric polyanioncompounds by oxidative polymerisation of 3,4-dialkoxythiophenes or3,4-alkylenedioxythiophenes according to the following formula:

wherein R¹ and R² are as defined above.

Stable aqueous polythiophene dispersions having a solids content of 0.05to 55% by weight and preferably of 0.1 to 10% by weight can be obtainedby dissolving thiophenes corresponding to the formula above, a polyacidand an oxidising agent in an organic solvent or preferably in water,optionally containing a certain amount of organic solvent, and thenstirring the resulting solution or emulsion at 0° C. to 100° C. untilthe polymerisation reaction is completed. The polythiophenes formed bythe oxidative polymerisation are positively charged, the location andnumber of such positive charges being not determinable with certaintyand therefore not mentioned in the general formula of the repeatingunits of the polythiophene polymer.

The oxidising agents are those which are typically used for theoxidative polymerisation of pyrrole as described in for example J. Am.Soc. 85, 454 (1963). Preferred inexpensive and easy-to-handle oxidisingagents are iron(III) salts, e.g. FeCl₃, Fe(ClO₄)₃ and the iron(III)salts of organic acids and inorganic acids containing organic residues.Other suitable oxidising agents are H₂O₂, K₂Cr₂O₇, alkali or ammoniumpersulphates, alkali perborates, potassium permanganate and copper saltssuch as copper tetrafluoroborate. Air or oxygen can also be used asoxidising agents. Theoretically, 2.25 equivalents of oxidising agent permol of thiophene are required for the oxidative polymerisation thereof(J. Polym. Sci. Part A, Polymer Chemistry, Vol. 26, p. 1287, 1988). Inpractice, however, the oxidising agent is used in excess, for example,in excess of 0.1 to 2 equivalents per mol of thiophene.

Polyanion

The polyacid forms a polyanion or, alternatively, the polyanion can beadded as a salt of the corresponding polyacids, e.g. an alkali salt.Preferred polyacids or salts thereof are polymeric carboxylic acids suchas poly(acrylic acid), poly((meth)acrylic acid) and poly(maleic acid) orpolymeric sulphonic acids such as poly(styrene sulphonic acid) orpoly(vinyl sulphonic acid). Alternatively, copolymers of such carboxylicand/or sulphonic acids and of other polymerizable monomers such asstyrene or acrylates can be used.

According to a twelfth embodiment of the material having a conductivepattern, according to the present invention, or a twelfth embodiment orthe material for making a conductive pattern, according to the presentinvention, the polyanion is poly(styrenesulphonate).

The molecular weight of these polyanion forming polyacids is preferablybetween 1000 and 2×10⁶, more preferably between 2000 and 5×10⁵. Thesepolyacids or their alkali salts are commercially available and can beprepared according to the known methods, e.g. as described inHouben-Weyl, Methoden der Organische Chemie, Bd. E20 MakromolekulareStoffe, Teil 2, (1987), pp. 1141.

Binders

In the materials having a conductive pattern and for making a conductivepattern, according to the present invention, the conductive element,surface elements and layers of the material, according to the presentinvention, may contain a binder.

According to a thirteenth embodiment of the material having a conductivepattern, according to the present invention, or a thirteenth embodimentor the material for making a conductive pattern, according to thepresent invention, the conductive element further contains a binder,e.g. polyvinyl alcohol and a vinylidene chloride, methyl methacrylate,itaconic acid (88/10/2) terpolymer.

According to a fourteenth embodiment of a material having a conductivepattern, according to the present invention, the type A surface elementhas an outermost layer with respect to the support containing aproteinaceous binder e.g. gelatin, casein, collagen, albumin, keratin,gluten, zein and modified gelatin e.g. acetylated or phthaloyl gelatin.

According to a fifteenth embodiment of a material having a conductivepattern, according to the present invention, the type A surface elementhas an outermost layer with respect to the support containing gelatin.

According to a sixteenth embodiment of a material having a conductivepattern, according to the present invention, the type B surface elementhas an outermost layer with respect to the support which is exclusive ofa proteinaceous binder and contains an optionally corona or glowdischarge treated polymer containing a monomeric unit selected from thegroup consisting of acrylates e.g. ethyl acrylate, acrylic acid,ethylene, ethylene glycol, formaldehyde, itaconic acid, melamine,methacrylates e.g. methyl methacrylate, methacrylic acid, optionallysubstituted isophthalic acid e.g. 5-sulpho-isophthalic acid andisophthalic acid, optionally substituted terephthalic acid e.g.terephthalic acid and vinylidene chloride. Examples of suitable polymersfor the outermost layer of type B surface element are:

PET = polyethylene terephthalate LATEX01 = vinylidene chloride, methylmethacrylate, itaconic acid (88/10/2) terpolymer, avail- able as 30%aqueous dispersion LATEX02 = a copolyester of 26.5 mol % terephthalicacid, 20 mol % isophthalic acid, 3.5 mol % 5-sulphoisophthalic acid and50 mol % ethylene glycol available as a 20% aqueous dispersion; LATEX03= a copolymer of 80% ethyl acrylate and 20% methacrylic acid availableas a 27% aqueous dispersion; HORDAMER ™ PE02 = polyethylene fromHOECHST, available as a 40% aqueous dispersion; PAREZ RESIN ™ 613 =melamine-formaldehyde resin from AMERICAN CYANAMID available as 80%solids;

Suitable binders for use in the material for making a conductivepattern, according to the present invention, are described in EP-A 564911 and include water-soluble polymers, such as poly(vinyl alcohol),water-soluble homo- and co-polymers of acrylic acid and homo- andco-polymers of methacrylic acid, and polymer latexes. Preferred bindersinclude poly(vinyl alcohol) and homo- and co-polymers of hydroxyethylmethacrylate and copolymers of 2-propenoic acid 2-phosphonooxy)ethylester, copolymers of 2-methyl-2-propenoic acid 2-phosphonooxy)ethylester. Such binders may be treated with a hardening agent, e.g. anepoxysilane such as 3-glycidyloxypropyltrimethoxysilane as described inEP-A 564 911, which is especially suitable when coating on a glasssubstrate.

According to a fourteenth aspect of the material for making a conductivepattern, according to the present invention, the outermost layer withrespect to the support of the type of surface element capable of beingat least partially removed by a developer is corona or glow dischargetreated polyethylene terephthalate.

According to a fifteenth aspect of the material for making a conductivepattern, according to the present invention, the outermost layer withrespect to the support of the type of surface element capable of beingat least partially removed by a developer contains polyethylene or amelamine-formaldehyde resin.

Examples of suitable polymers for use in the outermost layer withrespect to the support of the type of surface element capable of beingat least partially removed by a developer are: polyethyleneterephthalate surface treated with a corona discharge or with a glowdischarge, polyethylene, e.g. HORDAMER™ PE02, and melamine-formaldehyderesin, e.g. PAREZ RESIN™ 613.

According to a sixteenth aspect of the material for making a conductivepattern, according to the present invention, the outermost layer withrespect to the support of the type of surface element not capable ofbeing at least partially removed by a developer contains a polymerlatex.

According to a seventeenth aspect of the material for making aconductive pattern, according to the present invention, the outermostlayer with respect to the support of the type of surface element notcapable of being at least partially removed by a developer contains apolymer containing a monomer unit selected from the group consisting ofacrylates, acrylic acid, itaconic acid, methacrylates, methacrylic acidand vinylidene chloride.

According to an eighteenth aspect of the material for making aconductive pattern, according to the present invention, the outermostlayer with respect to the support of the type of surface element notcapable of being at least partially removed by a developer contains apolymer containing a monomer unit selected from the group consisting ofethylene glycol, optionally substituted isophthalic acid e.g.isophthalic acid and 5-sulpho-isophthalic acid, and optionallysubstituted terephthalic acid.

Examples of suitable polymers for use in the outermost layer withrespect to the support of the type of surface element not capable ofbeing at least partially removed by a developer are: LATEX01, LATEX02and LATEX03.

Additional Ingredients

The conductive element, surface elements and any layers of the material,according to the present invention, may contain various additionalingredients, such as one or more binders, one or more surfactants,spacing particles, UV-acutance compounds and IR-absorbers.

According to a seventeenth embodiment of the material having aconductive pattern, according to the present invention, or a nineteenthembodiment of the material for making a conductive pattern, according tothe present invention, the conductive element contains at least oneanionic or non-ionic surfactant.

According to an eighteenth embodiment of the material having aconductive pattern, according to the present invention, or a twentiethembodiment of the material for making a conductive pattern, according tothe present invention, the conductive element contains at least onenon-ionic surfactant selected from the group of surfactants consistingof ethoxylated/fluroralkyl surfactants, polyethoxylated siliconesurfactants, polysiloxane/polyether surfactants, ammonium salts ofperfluro-alkylcoarboxylic acids, polyethoxylated surfactants andfluorine-containing surfactants.

According to a nineteenth embodiment of the material having a conductivepattern, according to the present invention, or a twenty-firstembodiment or the material for making a conductive pattern, according tothe present invention, at least one type of the surface element containsat least one anionic or non-ionic surfactant.

Suitable non-ionic surfactants are:

Surfactant no. 01 = ZONYL ® FSN, a 40% by weight solution ofF(CF₂CF₂)₁₋₉CH₂CH₂O(CH₂CH₂O)_(x)H in a 50% by weight solution ofisopropanol in water where x = 0 to about 25, from DuPont; Surfactantno. 02 = ZONYL ® FSN-100: F(CF₂CF₂)₁₋₉CH₂CH₂O(CH₂CH₂O)_(x)H where x = 0to about 25, from DuPont; Surfactant no. 03 = ZONYL ® FS300, a 40% byweight aqueous solution of a fluorinated surfactant, from DuPont;Surfactant no. 04 = ZONYL ® FSO, a 50% by weight solution of a mixtureof ethoxylated non-ionic fluoro- surfactant with the formula:F(CF₂CF₂)₁₋₇CH₂CH₂O(CH₂CH₂O)_(y)H where y = 0 to ca. 15 in a 50% byweight solution of ethylene glycol in water, from DuPont; Surfactant no.05 = ZONYL ® FSO-100, a mixture of ethoxylated non-ionicfluoro-surfactant from DuPont with the formula:F(CF₂CF₂)₁₋₇CH₂CH₂O(CH₂CH₂O)_(y)H where y = 0 to ca. 15 from DuPont;Surfactant no. 06 = Tegoglide ® 410, a polysiloxane-polymer copolymersurfactant, from Goldschmidt; Surfactant no. 07 = Tegowet ®, apolysiloxane-polyester copolymer surfactant, from Goldschmidt;Surfactant no. 08 = FLUORAD ®FC431:CF₃(CF₂)₇SO₂(C₂H₅)N—CH₂CO—(OCH₂CH₂)_(n)OH from 3M; Surfactant no. 09 =FLUORAD ®FC126, a mixture of the ammonium salts of perfluorocarboxylicacids, from 3M; Surfactant no. 10 = polyoxyethylene-10-lauryl etherSuitable anionic surfactants are: Surfactant no. 11 = ZONYL ® 7950, afluorinated surfactant, from DuPont; Surfactant no. 12 = ZONYL ® FSA,25% by weight solution of F(CF₂CF₂)₁₋₉CH₂CH₂SCH₂CH₂COOLi in a 50% byweight solution of isopropanol in water, from DuPont; Surfactant no. 13= ZONYL ® FSE, a 14% by weight solution of [F(CF₂CF₂)₁₋₇CH₂CH₂O]_(x)P(O)(ONH₄)_(y) where x = 1 or 2; y = 2 or 1; and x + y = 3 in a 70% byweight solution of ethylene glycol in water, from DuPont; Surfactant no.14 = ZONYL ® FSJ, a 40% by weight solution of a blend of[F(CF₂CF₂)₁₋₇CH₂CH₂O]_(x)P(O) (ONH₄)_(y) where x = 1 or 2; y = 2 or 1;and x + y = 3 with a hydrocarbon surfactant in 25% by weight solution ofisopropanol in water, from DuPont; Surfactant no. 15 = ZONYL ® FSP, a35% by weight solution of [F(CF₂CF₂)₁₋₇CH₂CH₂O]_(x)P(O) (ONH₄)_(y) wherex = 1 or 2; y = 2 or 1 and x + y = 3 in 69.2% by weight solution ofisopropanol in water, from DuPont; Surfactant no. 16 = ZONYL ® UR:[F(CF₂CF₂)₁₋₇CH₂CH₂O]_(x)P(O) (OH)_(y) where x = 1 or 2; y = 2 or 1 andx + y = 3, from DuPont; Surfactant no. 17 = ZONYL ® TBS: a 33% by weightsolution of F(CF₂CF₂)₃₋₈CH₂CH₂SO₃H in a 4.5% by weight solution ofacetic acid in water, from DuPont; Surfactant no. 18 = Ammonium salt ofperfluoro-octanoic acid;

Multidiazonium Salts

A multidiazonium salt is a salt with at least two groups with twonitrogen atoms bonded together with a double or triple bond, such groupsincluding —N≡N⁺ and —N═N—R groups, e.g. —N═N—SO₃M groups e.g.bisdiazonium salts, trisdiazonium salts, tetrakisdiazonium salts,bis(aryldiazosulphonate) salts, tris(aryldiazosulphonate) salt andterakis(bis(aryldiazosulphonate) salts.

Upon exposure the adhesion of a conductive element containing amultidiazonium salt to the patterned surface is increased (due to thedestruction of the diazonium groups) and additionally the photolysisproducts of the diazo may increase the level of crosslinking of thepolymeric binder or resin comprising a multidiazonium salt if present.Combinations of multidiazonium salts can also be used.

Bisdiazonium salts for use in the material for making a conductivepattern, according to the present invention, include: benzidinetetrazoniumchloride, 3,3′-dimethylbenzidine tetrazoniumchloride,3,3′-dimethoxybenzidine tetrazoniumchloride, 4,4′-diaminodiphenylaminetetrazoniumchloride, 3,3′-diethylbenzidine tetrazoniumsulphate,4-aminodiphenylamine diazoniumsulphate, 4-aminodiphenylaminediazoniumchloride, 4-piperidino aniline diazoniumsulphate,4-diethylamino aniline diazoniumsulphate and oligomeric condensationproducts of diazodiphenylamine and formaldehyde.

According to a twenty-second embodiment of a material for making aconductive pattern, according to the present invention, the conductiveelement further contains a multidiazonium salt, a resin comprising adiazonium salt or both a multidiazonium salt and a resin comprising adiazonium salt, which reduces the removability of those parts of theconductive element contiguous with the patterned surface not removedduring the development step. Combinations of resins comprising adiazonium salt can also be used.

According to a twenty-third embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement contains a bis(aryldiazosulphonate) salt, atris(aryldiazosulphonate) salt or a tetrakis(aryldiazosulphonate) salt.

According to a twenty-fourth embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a bis(aryldiazosulphonate) salt, which reducesthe removability of exposed parts of the outermost layer, according toformula (II):

 MO₃S—N═N—Ar—L—Ar—N═N—SO₃M  (II)

where Ar is a substituted or unsubstituted aryl group, L is a divalentlinking group, and M is a cation. L preferably represents a substitutedor unsubstituted divalent aryl group or a substituted or unsubstitutedsaturated or unsaturated alkylene group, whose chain is optionallysubstituted with at least one of an oxygen atom, a sulphur atom or anitrogen atom. Ar preferably represents an unsubstituted phenyl group ora phenyl group substituted with one or more alkyl groups, aryl groups,alkoxy groups, aryloxy groups or amino groups. M preferably represents acation such as NH₄ ⁺ or a metal ion such as a cation of Al, Cu, Zn, analkaline earth metal or alkali metal.

Resins Comprising a Diazonium Salt

The term resin comprising a diazonium salt means a resin with groupswith two nitrogen atoms bonded together with a double or triple bond,such groups including —N≡N⁺ and —N═N—R groups e.g. —N═N—SO₃M groups.Suitable resins comprising a diazonium salt, according to the presentinvention, include polymers or copolymers of an aryldiazosulphonate andcondensation products of an aromatic diazonium salt. Such condensationproducts are described, for example, in DE-P-1 214 086.

Upon exposure the conductive element containing resins comprising adiazonium salt exhibits increased adhesion to the patterned surface andadditionally the photolysis products of the diazo may increase the levelof crosslinking of the polymeric binder or resin comprising a diazoniumsalt.

According to a twenty-fifth embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a polymer or copolymer of anaryldiazosulphonate.

According to a twenty-sixth embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a polymer or copolymer of anaryldiazosulphonate represented by formula (III):

wherein R⁰, R¹ and R² each independently represent hydrogen, an alkylgroup, a nitrile or a halogen, e.g. Cl, L represents a divalent linkinggroup, n represents 0 or 1, A represents an aryl group and M representsa cation. L preferably represents divalent linking group selected fromthe group consisting of: —(X)_(t)—CONR³—, —(X)_(t)—COO—, —X— and—(X)_(t)—CO—, wherein t represents 0 or 1; R³ represents hydrogen, analkyl group or an aryl group; X represents an alkylene group, an arylenegroup, an alkylenoxy group, an arylenoxy group, an alkylenethio group,an arylenethio group, an alkylenamino group, an arylenamino group,oxygen, sulphur or an aminogroup. A preferably represents anunsubstituted aryl group, e.g. an unsubstituted phenyl group or an arylgroup, e.g. phenyl, substituted with one or more alkyl groups, arylgroups, alkoxy groups, aryloxy groups or amino groups. M preferablyrepresents a cation such as NH₄ ⁺ or a metal ion such as a cation of Al,Cu, Zn, an alkaline earth metal or alkali metal.

Polymers and copolymers of an aryldiazosulphonate can be prepared byhomo- or copolymerization of aryldiazosulphonate monomers with otheraryldiazosulphonate monomers and/or with vinyl monomers such as(meth)acrylic acid or esters thereof, (meth)acrylamide, acrylonitrile,vinylacetate, vinylchloride, vinylidene chloride, styrene, alpha-methylstyrene etc. A particularly preferred comonomer ishydroxyethylmethacrylate. Specific examples of suitablearyldiazosulphonate polymers are described in EP-A 771 645.

Combination of a Multidiazonium Salt and a Resin Comprising a DiazoniumSalt

According to a twenty-seventh embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a combination of a resin comprising anaryldiazosulphonate and a bis(aryldiazosulphonate) salt.

According to a twenty-eighth embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a combination of a resin comprising anaryldiazosulphonate and a bis(aryldiazosulphonate) salt in the molarpercentage ratio range of 60%/40% to 10%/90%.

According to a twenty-ninth embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a combination of a resin comprising anaryldiazosulphonate and a bis(aryldiazosulphonate) salt in the molarpercentage ratio range of 50%/50% to 20%/80%.

According to a thirieth embodiment of the material for making aconductive pattern, according to the present invention, the conductiveelement further contains a combination of a copolymer ofhydroxyethylmethacrylate andsodium-4-methacryloyl-aminophenyl-diazo-sulphonate and abis(aryldiazosulphonate) salt.

Production Process for Materials of Present Invention

In the production of the materials of the present invention, the coatingdispersions or solutions may be applied by any means known in the art:they can be spin-coated, sprayed or coated by any of the continuouscoating techniques that are used to coat solutions on continuous webs,e.g. dip coating, rod coating, blade coating, air knife coating, gravurecoating, reverse roll coating, extrusion coating, slide coating andcurtain coating. An overview of these coating techniques can be found inthe book “Modern Coating and Drying Technology”, Edward Cohen and EdgarB. Gutoff Editors, VCH publishers, Inc, New York, N. Y., 1992. It isalso possible to coat simultaneously multiple layers by coatingstechnique such as slide coating and curtain coating. It is also possibleto apply the coating solutions and dispersions by printing techniques,e.g., ink-jet printing, gravure printing, flexo printing, or offsetprinting.

The coating solution or dispersion containing the intrinsicallyconductive polymer is preferably applied to the substrate in such anamount that the coated polymer layer contains between 10 and 5000 mg ofintrinsically conductive polymer per m², more preferably between 100 and500 mg of intrinsically conductive polymer per m².

The coating dispersion or solution of a polyanion and an intrinsicallyconductive polymer of the conductive element preferably also comprisesan organic compound that is: a linear, branched or cyclic aliphaticC₂₋₂₀ hydrocarbon or an optionally substituted aromatic C₆₋₁₄hydrocarbon or a pyran or a furan, the organic compound comprising atleast two hydroxy groups or at least one —COX or —CONYZ group wherein Xdenotes —OH and Y and Z independently of one another represent H oralkyl; or a hetero-cyclic compound containing at least one lactam group.Examples of such organic compounds are e.g. N-methyl-2-pyrrolidinone,2-pyrrolidinone, 1,3-dimethyl-2-imidazolidone,N,N,N′,N′-tetramethyl-urea, formamide, dimethylformamide, andN,N-dimethylacetamide. Preferred examples are sugar or sugar derivativessuch as arabinose, saccharose, glucose, fructose and lactose, or di- orpolyalcohols such as sorbitol, xylitol, mannitol, mannose, galactose,sorbose, gluconic acid, ethylene glycol, di- or tri(ethylene glycol),1,1,1-trimethylol-propane, 1,3-propanediol, 1,5-pentanediol,1,2,3-propantriol, 1,2,4-butantriol, 1,2,6-hexantriol, or aromatic di-or polyalcohols such as resorcinol.

Exposure Process

Subsequent to processing the material of the present invention with adeveloper to remove at least partially those parts of the conductiveelement contiguous with one type of surface elements, the material ofthe present invention can be exposed to ultraviolet light optionally incombination with blue light in the wavelength range of 250 to 500 nm orinfrared light. Useful exposure sources are high or medium pressurehalogen mercury vapour lamps, e.g. of 1000 W or lasers having anemission wavelength in the range from about 700 to about 1500 nm, suchas a semiconductor laser diode, a Nd:YAG laser or a Nd:YLF laser.

Development Process

The material of the present invention is developed in a developer whichcan be deionized water or is preferably water-based. During developmentthose parts of the conductive element contiguous with one type ofsurface elements of the patterned surface are at least partially removedand a conductive pattern is thereby obtained. Suitable aqueousdevelopers are deionized water, AZ303 (Clariant) or EN232 (AGFA-GEVAERTN.V.). When a subbing layer (also called substrate layer) is present onthe support the material is preferably rubbed thoroughly with a tissueduring development to avoid residual conductivity. The rubbing can bedone in the processing fluid or in a separate water bath after thedevelopment stage. Similar results can be obtained by applying a highpressure water jet after the development stage, thereby avoiding contactwith the conductive areas. Alternatively, if conductivity enhancement isnecessary, the developer can contain the conductivity enhancement agent,thereby combining the steps of development and contact with theconductivity enhancement agent.

Industrial Application

The conductive pattern obtained by the method of the present inventioncan be used as an electronic circuit for making an electric orsemiconductor device such as a printed circuit board, an integratedcircuit, a display, an electroluminescent device or a photovoltaic cell.The patterned electrode obtained by the method of the present inventioncan also be used for screening electromagnetic radiation or earthingelectric charges, for making touch screens, radio frequencyidentification tags, electrochromic windows and in imaging systems, e.g.silver halide photography or electrophotography. Also a device such asthe electronic book described in WO 97/04398 may particularly benefitfrom the flexible electrode of the present invention. Even moreapplications are described in WO 97/18944.

While the present invention will hereinafter be described in connectionwith preferred embodiments thereof, it will be understood that it is notintended to limit the invention to those embodiments. All percentagesgiven in the EXAMPLES are percentages by weight unless otherwise stated.

EXAMPLES

Ingredients used in the conductive element which are not mentioned aboveare:

PEDOT = poly(3,4-ethylenedioxythiophene) PSS = poly(styrenesulphonicacid) NDP01 = homopolymer of

Ingredients used in the subbing layers not mentioned above:

KIESELSOL 100F = a colloid silica from BAYER, available as a 30% aqueousdispersion; KIESELSOL 300F = a colloidal silica from BAYER, available asa 30% aqueous dispersion; ARKOPON ™ T = a sodium salt ofN-methyl-N-2-sulfoethyl- oleylamide by HOECHST a surfactant fromHOECHST, supplied as a 40% concentrate; MERSOLAT ™ H76 = a sodiumpentadecylsulfonate by BAYER, supplied as a 76% concentrate; ULTRAVON ™W = a sodium arylsulfonate from CIBA-GEIGY, supplied as a 75-85%concentrate; ARKOPAL ™ N060 = a nonylphenylpolyethylene-glycol fromHOECHST;The 100 μm polyethylene terephthalate (PET) film used in the was treatedas follows:

Treatment nr. Layer composition 01 79.1% LATEX01; 18.6% KIESELSOL ™100F; 0.5% MERSOLAT ™ H; and 1.9% ULTRAVON ™ W 02 surface treated with acorona discharge 03 surface treated with an glow discharge 04 layercombination consisting of a 1st layer of 79.1% LATEX01; 18.6%KIESELSOL ™ 100F; 0.5% MERSOLAT ™ H; and 1.9% ULTRAVON ™ W; and a 2ndlayer consisting of 49% gelatin, 44% KIESELSOL ™ 300F, 1.72% ULTRAVON ™W, 0.86% ARKOPAL ™ N060, 2.86% hexylene glycol, 1.43% trimethylolpropane and 0.13% of 3 μm polymethyl methacylate particles 05 77.2% ofLATEX02; 5.8% of LATEX03; 1.3% HORDAMER ™ PE02 and 14.6% PAREZ RESIN ™613. 06 layer combination consisting of a first layer of 85.6% ofLATEX01, 9.5% of KIESELSOL ™ 100F, 2.5% of PEDOT/PSS, 0.5% of MERSOLAT ™76H and 1.9% ULTRAVON ™ W; and a second layer consisting of 49% gelatin,44% KIESELSOL ™ 300F, 1.72% ULTRAVON ™ W, 0.86% ARKOPAL ™ N060, 2.86%2-methyl-2,4- pentanediol, 1.43% trimethylol propane and 0.13% of 3 μmpolymethyl methacylate particles 07 79.8% LATEX02; 19.9% KIESELSOL ™100F; and 0.3% ARKOPON ™ T 08 75.0% LATEX01, 9.0% LATEX03 and 16.0%KIESELSOL ™ 100FFor the corona discharge treatment of PET film in air, an AHLBRANDT™corona treater type 53-02 was used consisting of 2 quartz electrodes, agrounded treater roll and a 15 kHz generator. The air gap between theelectrode and film was 1.2 mm and the film as endowed with optimaladhesion properties by transporting it at a speed of 10 m/min under thecorona treater at a watt density of 400 Wmin/m².

The glow discharge treatment of PET film was carried out in a vacuumsystem consisting of a reactor vessel, vacuum pumps, a gas inlet, a DCpower source and a titanium glow cathode. The operating conditions usedwere a transport speed of 40 m/min, an air pressure of 10⁻² mbar and apower density of 40 Wmin/m² and a distance between the cathode and filmof 100 mm.

PEDOT/PSS Dispersion

The aqueous dispersions of PEDOT/PSS in a weight ratio of 1:2.4 used inthe EXAMPLES were prepared according to the method described in EP-A 1079 397. The particle size of the PEDOT/PSS latex was determined by CPSdisc centrifuge measurements to be narrow with a maximum at 25 nm and anaverage particle size of 30-50 nm.

Example 1

In EXAMPLE 1, the conductive element consisted of PEDOT/PSS and ZONYL™FSO 100 and was coated from a dispersion containing N-methylpyrrolidinone and diethylene glycol for Samples I and II respectively.Samples I and II were produced by coating 40 mL/m² of the dispersiongiven in Table 1 on a PET support partially with treatment nr. 03 (IAand IIA) and partially with treatment nr. 04 (IB and IIB) to a wetthickness of 50 μm. After drying Samples I and II for 10 minutes at 50°C. and 20 minutes at 110° C. respectively they had the compositionsgiven in Table 1.

TABLE 1 composition of the coating dispersions SAMPLE SAMPLE IA IB IIAIIB Treatment nrs. INGREDIENT [mL] 03 04 03 04 1.2% aqueous dispersionof 16.7 16.7 12.5 12.5 PEDOT/PSS 2% aqueous solution of 0.50 0.50 0.500.50 ZONYL ™ FSO 100 N-methyl-pyrrolidinone 2.50 2.50 — — diethyleneglycol — — 2.75 2.75 deionized water 30.30 30.30 34.25 34.25 COVERAGE[mg/m²] PEDOT/PSS 200 200 150 150 ZONYL FSO 100 10 10 10 10The surface resistances of the parts of the PEDOT/PSS-containingconductive element contiguous with treatment nr. 03 and those contiguouswith treatment nr. 04 were determined as described above and the resultsare given in Table 2.

TABLE 2 SAMPLES PROPERTY I II R_(s) (Ω/square) of conductive elementcontiguous 3.4 × 10⁴ 3.55 × 10³ with treatment nr. 04 R_(s) (Ω/square)of conductive element contiguous 1.0 × 10³  1.4 × 10³ with treatment nr.03 R_(s) ratio of parts of conductive element contig- 34 2.5 uous withtreatment nr. 04/parts of conductive element contiguous with treatmentnr. 03A R_(s) ratio of parts of conductive element contiguous with treatmentnr. 04/parts of conductive element contiguous with treatment nr. 03 was34 with sample I and 2.5 with samples II, showing the strong influenceof choice of conductivity-enhancing agent on the R_(s)-ratio observed.In both cases a conductive pattern was realized.

Example 2

In EXAMPLE 2, the conductive element consisted of PEDOT/PSS, NDP01 andZONYL™ FSO 100 and was coated from a dispersion containing N-methylpyrrolidinone. Sample III was produced by coating 40 mL/m² of thedispersion given in Table 3 on a PET support partially with treatmentnr. 01 (IIIA) and partially with treatment nr. 04 (IIIB) to a wetthickness of 40 μm. After drying the conductive elements of Sample IIIhad the compositions given in Table 3.

TABLE 3 composition of the coating dispersions SAMPLE IIIA IIIBTreatment nrs. INGREDIENT [mL] 01 04 1.2% aqueous dispersion ofPEDOT/PSS 1668 1668 17.8% by weight aqueous solution of NDP01 56 56 2%aqueous solution of ZONYL ™ FSO 100 40 40 N-methyl-pyrrolidinone 200 200deionized water 2036 2036 COVERAGE [mg/m²] PEDOT/PSS 200 200 NDP02 100100 ZONYL ™ FSO 100 8 8The surface resistances of the parts of the PEDOT/PSS-containingconductive element contiguous with treatment nr. 01 and those contiguouswith treatment nr. 04 were determined as described above and the resultsare given in Table 4.

TABLE 4 PROPERTY R_(s) (Ω/square) of conductive element contiguous with1.8 × 10⁵ treatment nr. 04 (SAMPLE IIIB) R_(s) (Ω/square) of conductiveelement contiguous with 5.2 × 10³ treatment nr. 01 (SAMPLE IIIA) R_(s)ratio of parts of conductive element contiguous with 34.6 treatment nr.04/parts of conductive element contiguous with treatment nr. 01A R_(s) ratio of parts of conductive element contiguous with treatmentnr. 04/parts of conductive element contiguous with treatment nr. 01 of34.6 showed that a conductive pattern had been realized. The presence ofthe diazosulphonate copolymer NDP01 slightly increased the surfaceresistance values.

Example 3

In EXAMPLE 3, the conductive element consisted of PEDOT/PSS and ZONYL™FSO 100 and was coated from dispersions containing N-methylpyrrolidinone. Samples IV to VII were produced by coating to the wetthicknesses given in Table 5 on PET supports with treatment nrs. 3 and4. After drying the Samples IV to VII had the compositions also given inTable 5.

TABLE 5 composition of the coating dispersions SAMPLE IV V VI VIITreatment nr. INGREDIENT [mL] 3/4 3/4 3/4 3/4 1.2% aqueous dispersion of16.70 20.83 41.66 41.66 PEDOT/PSS 2% aqu. solution of ZONYL ™ 0.50 0.500.50 0.50 FSO 100 N-methyl-pyrrolidinone 2.50 3.12 6.24 6.24 deionizedwater 30.3 30.3 30.3 30.3 WET COVERAGE [μm] 50 100 100 200 DRY COVERAGE[mg/m²] PEDOT/PSS 200 500 1000 2000 ZONYL ™ FSO 100 10 20 20 40The surface resistances of SAMPLES IV to VII were determined asdescribed above and the results are given in Table 6.

TABLE 6 SAMPLE PROPERTY IV V VI VII Thickness of electroconductive 200500 1000 2000 layer [nm] R_(s) (Ω/square) of conductive element 3.4 ×675 200 95 contiguous with treatment nr. 04 10⁴ R_(s) (Ω/square) ofconductive element 1.0 × 440 185 83 contiguous with treatment nr. 03 10³R_(s) ratio of parts of conductive element  34 1.5 1.1 1.1 contiguouswith treatment nr. 04/parts of conductive element contiguous withtreatment nr. 03.From Table 6 it can be seen that the influence of the support on thesurface resistance decreased considerably with increasing layerthickness, no significant effect being observed at layer thicknessesgreater than 500 nm.

Example 4

In EXAMPLE 4, the conductive element consisted of PEDOT/PSS, NDP01 andZONYL™ FSO 100 and was coated from a dispersion containing N-methylpyrrolidinone. Samples VIII to XV were produced by coating 40 mL/m² ofthe dispersions given in Table 7 on Support nr. 1 to 8 to a wetthickness of 40 μm. After drying the Samples VIII to XV had thecompositions also given in Table 7.

TABLE 7 composition of the coating dispersions INGREDIENT SAMPLE [mL]VIII IX X XI XII XIII XIV XV Treatment nr. 1 2 3 4 5 6 7 8 1.2% aqueous1668 1668 1668 1668 1668 1668 1668 1668 dispersion of PEDOT/PSS 17.8%aq. sol. 56 56 56 56 56 56 56 56 of NDP01 2% aqueous 40 40 40 40 40 4040 40 solution of ZONYL ™ FSO 100 N-methyl- 200 200 200 200 200 200 200200 pyrrolidinone deionized water 2036 2036 2036 2036 2036 2036 20362036 COVERAGE [mg/m²] PEDOT/PSS 200 200 200 200 200 200 200 200 NDP02100 100 100 100 100 100 100 100 ZONYL ™ 8 8 8 8 8 8 8 8 FSO 100The surface resistances of SAMPLES VIII to XV were determined asdescribed above and the results are given in Table 8. The Samples werethen processed in water (softly rubbing with a tissue under water) anddried and the surface resistances determined. The results afterprocessing in water are also given in Table 8.

From Table 8 it can be seen that the PEDOT/PSS-containing conductiveelement contiguous with surface elements containing gelatin (treatmentnrs. 4 and 6) exhibited considerably higher surface resistances than thePEDOT/PSS-containing conductive element contiguous with surface elementsnot containing gelatin.

TABLE 8 SAMPLE PROPERTY VIII IX X XI XII XIII XIV XV Treatment nr 1 2 34 5 6 7 8 R_(s) (Ω/square) of 5.2 × 10³ 3.8 × 10³ 3.8 × 10³ 1.8 × 10⁵4.1 × 10³ 2.5 × 10⁵ 4.0 × 10³ 9.7 × 10³ coated layer before processingR_(s) (Ω/square) of 4.2 × 10⁵  6.5 × 10¹²  6.2 × 10¹² 9.9 × 10⁸  3.8 ×10¹² 9.0 × 10⁶ 9.6 × 10⁵ 1.1 × 10⁵ coated layer after processing

The results given in Table 8 also indicate that the particular supportused had a crucial effect on the surface resistance of the layer afterprocessing with water. In the cases of treatment nrs 1, 7 and 8 only amarginal increase in surface resistance was observed, indicating thatthe layer was incompletely removed although under a microscope the layerappeared to have been removed, whereas in the cases of treatment nrs 2,3 and 5 (Samples IX, X and XII) surface resistances of ca. 5×10¹²Ω/square were observed, indicating a more complete removal of the layer.Therefore, a potential R_(s) ratio after processing of 10⁷ is achievableusing two types of surface element.

In the cases of samples VIII, XIII, XIV and XV coated on treatment nrs1, 6, 7 and 8 surface resistances >10⁷ Ω/square could be obtained byrubbing thoroughly with a tissue during processing (results not shown inTable 8). However, subsequent exposure on a PRINTON™ CDL 1502i UVcontact exposure unit (from AGFA-GEVAERT N.V.) for 200 s at 2 mW/cm²(=exposure of 0.4 J/cm²) resulted in strongly increased adhesion withoutsignificant increase in surface resistance.

The present invention may include any feature or combination of featuresdisclosed herein either implicitly or explicitly or any generalisationthereof irrespective of whether it relates to the presently claimedinvention. In view of the foregoing description it will be evident to aperson skilled in the art that various modifications may be made withinthe scope of the invention.

1. A material having a conductive pattern, said material comprising asupport and a conductive element, said conductive element being 500 nmthick or less and containing a polyanion and an intrinsically conductivepolymer, characterized in that one surface of said conductive element isan outermost surface of said material and said other surface of saidconductive element is contiguous with a patterned surface, saidpatterned surface consisting of at least two types of surface element,and those parts of said conductive element contiguous with a type Asurface element exhibiting a surface resistance at least a factor of tengreater than those parts of said conductive element contiguous with atype B surface element.
 2. Material having a conductive patternaccording to claim 1, wherein said conductive pattern is anelectroconductive pattern.
 3. Material having a conductive patternaccording to claim 1, wherein said type A surface element has anoutermost layer with respect to said support containing a proteinaceousbinder.
 4. Material having a conductive pattern according to claim 3,wherein said proteinaceous binder is gelatin.
 5. Material having aconductive pattern according to claim 1, wherein said type B surfaceelement has an outermost layer with respect to said support which isexclusive of a proteinaceous binder and contains an optionally corona orglow discharge treated polymer containing a monomeric unit selected fromthe group consisting of acrylates, acrylic acid, ethylene, ethyleneglycol, formaldehyde, itaconic acid, melamine, methacrylates,methacrylic acid, optionally substituted isophthalic acid, optionallysubstituted terephthalic acid and vinylidene chloride.
 6. Materialaccording to claim 1, wherein said patterned surface is planar ornon-planar.
 7. Material according to claim 6, wherein said planarpatterned surface is the surface of said support or a patternwisetreated continuous layer.
 8. Material according to claim 7, wherein saidpatternwise treatment is carried out with a corona discharge or a glowdischarge.
 9. Material according to claim 6, wherein said non-planarpatterned surface consists of a non-continuous layer provided on acontinuous layer or on said support.
 10. Material according to claim 1,wherein said conductive element further contains a multidiazonium salt,a resin comprising a diazonium salt or both a multidiazonium salt and aresin comprising a diazonium salt.
 11. Material according to claim 1,wherein said intrinsically conductive polymer is a polymer or copolymerof a substituted or unsubstituted thiophene.
 12. Material according toclaim 11, wherein said polymer of a substituted or unsubstitutedthiophene is represented by formula (I):

in which n is larger than 1 and each of R¹ and R² independentlyrepresent hydrogen or an optionally substituted C₁₋₄ alkyl group ortogether represent an optionally substituted C₁₋₄ alkylene group or anoptionally substituted cycloalkylene group, preferably an ethylenegroup, an optionally alkyl-substituted methylene group, an optionallyC₁₋₁₂ alkyl- or phenyl-substituted ethylene group, a 1,3-propylene groupor a 1,2-cyclohexylene group.
 13. Material according to claim 1, whereinsaid polyanion is poly(styrenesulphonate).